Composition for organic electronic element encapsulant and encapsulant formed using same

ABSTRACT

A composition for an encapsulant according to an exemplary embodiment of the present invention comprises: 1) a first copolymer comprising the first unit represented by Chemical Formula 1, the second unit represented by Chemical Formula 2, and the third unit represented by Chemical Formula 3; 2) a second copolymer comprising the second unit represented by Chemical Formula 2 and the third unit represented by Chemical Formula 3; 3) one or more photoinitiators; and 4) a compound capable of dissolving the photoinitiators.

This application claims priority to and the benefit of Korean PatentApplication No. 10-2016-0167678 filed in the Korean IntellectualProperty Office on Dec. 9, 2016, the entire contents of which areincorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a composition for an organic electronicdevice encapsulant and an encapsulant formed by using the same.

BACKGROUND ART

In general, organic electronic devices are devices characterized in thata phenomenon such as light emission or a flow of electricity occurs whencharges are injected into an organic layer provided between a positiveelectrode and a negative electrode, and it is possible to manufacture adevice which serves various functions according to the organic materialselected.

As a representative example, organic light emitting diodes (OLEDs) havedrawn attention in the next-generation flat panel display field, theflexible display field, the lighting field, and the like because theOLEDS are thin and lightweight and have excellent color impression, andmay be manufactured on a glass substrate, an inorganic materialsubstrate comprising silicon, a metal substrate, and a flexiblesubstrate such as a plastic substrate or a metal foil in the relatedart. These organic electronic devices are extremely vulnerable tomoisture and oxygen and thus have a disadvantage in that light emittingefficiency and a service life are significantly reduced when the devicesare exposed to the air or when moisture is introduced into the inside ofa panel from the outside.

The encapsulation technology is an essential process for preventingoxidation of a light emitting material and an electrode material byblocking moisture and oxygen introduced from the outside of an OLED, andfurthermore, for protecting the device from mechanical and physicalimpacts applied from the outside of the device.

In order to solve the aforementioned problem, attempts have been made toblock moisture and oxygen introduced from the outside by using anencapsulant film using a glass cap or a metal cap or a laminating methodor depositing inorganic materials.

However, the glass cap has disadvantages in that costs caused by glassprocessing are increased due to implementing a large area of a panel,and there is a problem with implementing a large area thereof due tomechanical damage, and the like, and also has difficulties inmanufacturing a flexible OLED panel which requires flexibility. Themetal cap has a problem with a process caused by a difference in thermalexpansion coefficient between the metal cap and a substrate. Further, abonding film using the laminating method has a problem in that moistureand oxygen are introduced through an interface with a bonding surface ofthe film.

Furthermore, when using a metal cap method in which a moisture absorbentis provided inside a panel during the encapsulation of the organicelectronic device, an extension portion which protrudes at apredetermined height is formed in a metal cap structure for using amoisture absorbent, and when the metal cap is lastly bonded to asubstrate using a bonding agent, or an organic light emitting diode isencapsulated by processing glass to form a glass cap, a method ofbonding the metal cap to the substrate by using a method, such as sandblast or etching, to provide a moisture absorbent inside a predeterminedgroove is used. The method in the related art makes it difficult toprocess the metal cap due to an expansion of a space inside theencapsulation when a panel becomes large, and may cause a problem inthat the glass cap is easily broken by external pressure.

There is a need for developing a new encapsulation technology which isdifferent from the existing encapsulation process due to thesedifficulties.

DISCLOSURE Technical Problem

The present invention has been made in an effort to provide acomposition capable of preparing an encapsulant which may improve aservice life of an organic electronic device and effectively blockoxygen or moisture, and the like, which are introduced from the outside,and an encapsulant using the same.

Technical Solution

An exemplary embodiment of the present invention provides a compositionfor an encapsulant, comprising:

1) a first copolymer comprising a first unit represented by thefollowing Chemical Formula 1, a second unit represented by the followingChemical Formula 2, and a third unit represented by the followingChemical Formula 3;

2) a second copolymer comprising the second unit represented by thefollowing Chemical Formula 2 and the third unit represented by thefollowing Chemical Formula 3;

3) one or more photoinitiators; and

4) a compound capable of dissolving the photoinitiators.

In Chemical Formulae 1 to 3,

R1 is a direct bond, or an alkylene group,

R2 to R7 are the same as or different from each other, and may be eachindependently selected from the group consisting of hydrogen, an alkylgroup, an alkenyl group, an aryl group, a glycidyl group, an isocyanategroup, a hydroxy group, a carboxyl group, a vinyl group, an acrylategroup, a methacrylate group, an epoxide group, a cyclic ether group, asulfide group, an acetal group, a lactone group, an amide group, analkylaryl group, an alkylglycidyl group, an alkylisocyanate group, analkylhydroxy group, an alkylcarboxyl group, an alkylvinyl group, analkylacrylate group, an alkylmethacrylate group, an alkyl cyclic ethergroup, an alkylsulfide group, an alkylacetal group, an alkyl lactonegroup, and an alkyl amide group, and

a, b, c, and d are each independently 1 to 200.

Further, another exemplary embodiment of the present invention providesan encapsulant using the composition for an encapsulant.

Advantageous Effects

The composition for an encapsulant according to an exemplary embodimentof the present invention is characterized in that it is possible tomanufacture an encapsulant which may improve a service life of anorganic electronic device, and effectively block oxygen and moisture andthe like, which are introduced from the outside.

Further, the composition for an encapsulant according to an exemplaryembodiment of the present invention has a characteristic of improvingthe sensitivity of an encapsulant using the composition for anencapsulant by introducing a novel organopolysilicone-based resin suchas a first copolymer.

In particular, the composition for an encapsulant according to anexemplary embodiment of the present invention may improve thesensitivity during the UV curing by comprising a compound capable ofdissolving a photoinitiator to increase the amount of photoinitiatorintroduced. As described above, the composition for an encapsulantaccording to an exemplary embodiment of the present invention has acharacteristic of reducing an amount of outgas of a cured product afterthe curing by increasing the curing rate.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present application will be described in detail.

Organic EL devices are polycrystalline semiconductor devices, and areused for a liquid crystal backlight, and the like in order to obtainlight emission with high brightness at low voltage, and expected as athin-type flat display device. However, there are problems in thatorganic EL devices are extremely vulnerable to moisture, an interfacebetween a metal electric field and an organic EL layer may be peeled offdue to the effects of moisture, the resistance may be increased due tothe oxidation of metal, and organic materials may change in quality bymoisture, and as a result, the organic EL devices do not emit light, andbrightness thereof may deteriorate.

In order to solve the problems, methods for encapsulating an organic ELdevice have been developed. As the existing encapsulation methods, in anorganic EL device, there have been usually used a method of melting fritglass between a substrate and an upper glass plate by means of laser andbonding and hermetically sealing the edges of the two substrates, and asystem of inserting a moisture absorbent or a filler between a sealedglass plate and an organic EL device to remove moisture thereinside orincrease mechanical strength as a system of bonding the edge between asealed glass plate and an organic EL substrate by using a sealant.

However, an encapsulation technology using frit glass is a systemusually used in a small organic EL device, and a system of bonding theedge of a sealed glass plate by using a sealant has disadvantages inthat the strength is reduced and there occurs a warpage phenomenonduring a high heat process because there is an empty space between anorganic EL device and a glass plate. It is difficult to introduce theencapsulation method into the manufacturing of a flexible organic ELpanel, which requires the enlargement and flexibility of the organic ELdevice.

The present invention has been made in an effort to provide a curableencapsulant composition, which may prepare an encapsulant capable ofimproving a service life of an organic electronic device and effectivelyblocking oxygen and moisture, and the like, which are introduced fromthe outside, and may have process stability when a post-process isperformed by introducing a curable system, and an encapsulant using thesame.

In particular, the composition for an encapsulant according to anexemplary embodiment of the present invention may improve thesensitivity during the UV curing by comprising a compound capable ofdissolving a photoinitiator to increase the amount of photoinitiatorintroduced. As described above, the composition for an encapsulantaccording to an exemplary embodiment of the present invention has acharacteristic of reducing an amount of outgas of a cured product afterthe curing by increasing the curing rate.

A composition for an encapsulant according to an exemplary embodiment ofthe present invention comprises: 1) a first copolymer comprising thefirst unit represented by Chemical Formula 1, the second unitrepresented by Chemical Formula 2, and the third unit represented byChemical Formula 3; 2) a second copolymer comprising the second unitrepresented by Chemical Formula 2 and the third unit represented byChemical Formula 3; 3) one or more photoinitiators; and 4) a compoundcapable of dissolving the photoinitiators.

In the present invention, the first copolymer is characterized bycomprising: the first unit represented by Chemical Formula 1; the secondunit represented by Chemical Formula 2; and the third unit representedby Chemical Formula 3.

In general, a resin in which two oxygen atoms are bonded to one siliconeatom in a silicone-based resin refers to a D-type silicone-based resin,and a resin in which three oxygen atoms are bonded to one silicone atomin a silicone-based resin refers to a T-type silicone-based resin. Inthe related art, the D-type silicone-based resin or the T-typesilicone-based resin has been each independently used, or the D-typesilicone-based resin and the T-type silicone-based resin have been usedby being mixed with each other. However, a silicone-based resin such asthe first copolymer according to the present invention is not a mixtureof the D-type silicone-based resin and the T-type silicone-based resinas in the related art, but a silicone-based resin which comprises bothD-type and T-type in the silicone-based resin and is different from thatin the related art.

An exemplary embodiment of the present invention is characterized inthat suitable strength of a thin film for an encapsulant may be obtainedand the sensitivity may be improved during a curing process of acomposition for an encapsulant, by comprising both D-type and T-type ina silicone resin.

In an exemplary embodiment of the present invention, R2 of ChemicalFormula 1 may be a vinyl group, an acrylate group or a methacrylategroup, but is not limited thereto.

In an exemplary embodiment of the present invention, R3 to R7 ofChemical Formulae 2 and 3 may be each independently hydrogen or an alkylgroup, but are not limited thereto.

In the first copolymer, a weight ratio of the first unit represented byChemical Formula 1:the second represented by Chemical Formula 2:thethird unit represented by Chemical Formula 3 may be (1 to 30):(5 to80):(1 to 30) and (5 to 15):(10 to 50):(5 to 15), but is not limitedthereto.

The first copolymer may have a weight average molecular weight of 100 to1,000,000 and 1,000 to 50,000, but the weight average molecular weightis not limited thereto.

The content of the first copolymer may be 20 to 90 wt % and 30 to 70 wt% based on a total weight of the composition for an encapsulant, but isnot limited thereto.

In the present invention, the second copolymer is characterized bycomprising the second unit represented by Chemical Formula 2 and thethird unit represented by Chemical Formula 3. The second copolymer maybe a D-type silicone-based resin.

In the second copolymer, a weight ratio of the second unit representedby Chemical Formula 2:the third unit represented by Chemical Formula 3may be 1:1 to 100:1, 1:1 to 10:1, and 3:1 to 7:1, but is not limitedthereto.

The second copolymer may have a weight average molecular weight of 100to 1,000,000 and 1,000 to 50,000, but the weight average molecularweight is not limited thereto.

The content of the second copolymer may be 1 to 70 wt % and 5 to 60 wt %based on the total weight of the composition for an encapsulant, but isnot limited thereto.

An exemplary embodiment of the present invention is characterized inthat a suitable strength of an encapsulant thin film may be obtained andthe sensitivity may be improved during a curing process of anencapsulant composition, by applying both the first copolymer and thesecond copolymer.

In the present invention, the first copolymer and the second copolymermay be each independently a random copolymer.

In the present invention, the photoinitiator is thermally inactive, butgenerates free radicals when exposed to chemical rays. Examples of thephotoinitiator comprise a substituted or unsubstituted polynuclearquinone, which is a compound having two intra-cyclic carbon atoms amongthe conjugated carbon cyclic compounds, for example,2-benzyl-2-(dimethylamino)-1-(4-morpholino phenyl)-1-butanone,2,2-dimethoxy-2-phenylacetophenone, 9,10-anthraquinone,2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone,octamethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone,benz(benza)anthracene-7,12-dione, 2,3-naphthacene-5,12-dione,2-methyl-1,4-naphthoquinone, 1,4-dimethyl anthraquinone, 2,3-dimethylanthraquinone, 2-phenyl anthraquinone, 2,3-diphenyl anthraquinone,retenquinone, 7,8,9,10-tetrahydronaphthracene-5,12-dione, and1,2,3,4-tetrahydrobenz(tetrahydrobenza)-anthracene-7,12-dione, but arenot limited thereto.

The content of the photoinitiator may be 0.1 to 10 wt % based on thetotal weight of the composition for an encapsulant, but is not limitedthereto.

When the content of the photoinitiator is less than 0.1 wt % based onthe total weight of the composition for an encapsulant, there may occura problem in that even though strong ultraviolet rays are irradiatedthereon, curing does not proceed due to a small number of activeradicals which promotes the curing, and when the content exceeds 10 wt%, there is concern in that a service life of an organic light emittingdevice may be shortened because outgassing occurs under the temperatureconditions of less than 100° C. after the curing.

The compound capable of dissolving the photoinitiators may comprise acompound which does not cause an optical separation while being mixedwith a silicone resin. Specific examples of the compound capable ofdissolving the photoinitiators comprise an acrylate-based compound, amethacrylate-based compound, a siloxane-based compound, asilicone-acrylate-based compound, and the like, but are not limitedthereto. The compound capable of dissolving the photoinitiators ispreferably a compound having a functional group capable of beingcross-linked with a binder in order not to generate an outgas afterbeing applied to a device, and is preferably a compound having a weightaverage molecular weight of 1,000 or less, preferably 400 or less inorder to meet optical characteristics with a silicone resin. Examples ofthe compound capable of dissolving the photoinitiators comprisealpha-methacryloxy-gamma-butyrolactone, methyl methacrylate, hydroxymethyl methacrylate, styrene, adamantyl methyl methacrylate,1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate,1,3-propanediol dimethacrylate, 1,3-propanediol diacrylate, neopentylglycol dimethacrylate, neopentyl glycol diacrylate, ethylene glycoldimethacrylate, ethylene glycol diacrylate, diethylene glycoldimethacrylate, diethylene glycol diacrylate, pentaerythritoltriacrylate, pentaerythritol tetraacrylate, tetraethylene glycoldimethacrylate, tetraethylene glycol diacrylate, butanedioldimethacrylate, butanediol diacrylate, dipropylene glycoldimethacrylate, dipropylene glycol diacrylate, methacryloxymethyl-bis-trimethylsiloxy methylsilane,methacryloxymethyldimethylethoxysilane,methacryloxymethylphenyldimethylsilane,methacryloxypropyltrisethoxysilane, methacryloxytrimethyl silane,methacryloxytrimethylsilane, methacryloxypropyltris trimethylsiloxysilane, and the like, but are not limited thereto.

The content of the compound capable of dissolving the photoinitiatorsmay be 0.1 to 30 wt % based on the total weight of the composition foran encapsulant, but is not limited thereto because an amount of compoundused may be changed according to the solubility of the photoinitiatorused.

Further, the compound capable of dissolving the photoinitiators may berepresented by the following Chemical Formula 4 or 5, but is not limitedthereto.

In an exemplary embodiment of the present invention, the composition foran encapsulant may additionally comprise a reactive silicone-basedoligomer represented by the following Chemical Formula 6.

In Chemical Formula 6,

R9, R10, R12, and R16 are the same as or different from each other, andare each independently a direct bond or an alkylene group,

R8, R11, R13, R14, R15, and R17 are the same as or different from eachother, and may be each independently selected from the group consistingof hydrogen, an alkyl group, an alkenyl group, an aryl group, a glycidylgroup, an isocyanate group, a hydroxy group, a carboxyl group, a vinylgroup, an acrylate group, a methacrylate group, an epoxide group, acyclic ether group, a sulfide group, an acetal group, a lactone group,an amide group, an alkylaryl group, an alkylglycidyl group, analkylisocyanate group, an alkylhydroxy group, an alkylcarboxyl group, analkylvinyl group, an alkylacrylate group, an alkylmethacrylate group, analkyl cyclic ether group, an alkylsulfide group, an alkylacetal group,an alkyl lactone group, and an alkyl amide group, and

e is 1 to 100.

In an exemplary embodiment of the present invention, the reactivesilicone-based oligomer may have a weight average molecular weight of100 to 15,000, but the weight average molecular weight is not limitedthereto.

In an exemplary embodiment of the present invention, R11 and R13 ofChemical Formula 6 may be each independently a vinyl group, an acrylategroup or a methacrylate group, but are not limited thereto.

In an exemplary embodiment of the present invention, R8, R14, R15, andR17 of Chemical Formula 6 may be each independently hydrogen or an alkylgroup, but are not limited thereto.

According to an exemplary embodiment of the present invention, ChemicalFormula 6 may be represented by the following Chemical Formula 7.

In an exemplary embodiment of the present invention, the reactivesilicone-based oligomer may serve to adjust the surface leveling of anencapsulant of a composition for an encapsulant.

In an exemplary embodiment of the present invention, the composition foran encapsulant may comprise a first copolymer, a second copolymer, aphotoinitiator, a compound capable of dissolving the photoinitiator, anda reactive silicone-based oligomer. In this case, based on the totalweight of the composition for an encapsulant, the content of the firstcopolymer may be 20 to 60 wt %, the content of the second copolymer maybe 10 to 30 wt %, the content of the photoinitiator may be 0.1 to 10 wt%, the content of the compound capable of dissolving the photoinitiatorsmay be 5 to 30 wt %, and the content of the reactive silicone-basedoligomer may be 5 to 30 wt %, but the contents are not limited thereto.

The composition for an encapsulant according to an exemplary embodimentof the present invention may additionally comprise a monomer known inthe art in order to adjust a curing speed of the silicone resinmaterial. Specific examples of the monomer comprise an acrylate-basedmonomer, a methacrylate-based monomer, a siloxane-based monomer, and thelike, but are not limited thereto.

Examples of the monomer comprise triethylolpropane ethoxy triacrylate,t-butyl (meth)acrylate, 1,5-pentanediol di(meth)acrylate,N,N-diethylaminoethyl (meth)acrylate, ethylene glycol di(meth)acrylate,1,4-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate,hexamethylene glycol di(meth)acrylate, 1,3-propanediol di(meth)acrylate,decamethylene glycol di(meth)acrylate, 1,4-cyclohexanedioldi(meth)acrylate, 2,2-dimethylolpropane di(meth)acrylate, glyceroldi(meth)acrylate, tripropylene glycol di(meth)acrylate, glyceroltri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritoltri(meth)acrylate, polyoxyethylated trimethylolpropanetri(meth)acrylate, 2,2-di-(p-hydroxyphenyl)propane diacrylate,pentaerythritol tetra(meth)acrylatelate, 2,2-di-(p-hydroxyphenyl)propanedimethacrylate, triethylene glycol diacrylate,polyoxyethyl-2,2-di-(p-hydroxyphenyl)propane dimethacrylate,di-(3-methacryloxy-3-hydroxypropyl)ether of bisphenol-A,di-(2-methacryloxyethyl)ether of bisphenol-A,di-(3-acryloxy-2-hydroxypropyl)ether of bisphenol-A,di-(2-acryloxyethyl)ether of bisphenol-A,di-(3-methacryloxy-2-hydroxypropyl)ether of 1,4-butanediol, triethyleneglycol dimethacrylate, polyoxypropyltrimethylol propane triacrylate,butylene glycol di(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate,2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate,1-phenylethylene-1,2-dimethacrylate, diallyl fumarate, styrene,1,4-benzenediol dimethacrylate, 1,4-diisopropenyl benzene,1,3,5-triisopropenyl benzene, a silicone-based monomer, a siliconeacrylate-based monomer, a silicone urethane-based monomer, and the like,but are not limited thereto.

In addition, the composition for an encapsulant according to anexemplary embodiment of the present application may comprise one or moreadditives such as a curing catalyst, a viscosity adjusting agent, acuring agent, a dispersing agent, a stabilizer, and a curing promoterdepending on the use thereof. These additives may be used either aloneor in mixture of two or more thereof.

Furthermore, an encapsulant according to an exemplary embodiment of thepresent invention is characterized by using the composition for anencapsulant. More specifically, the encapsulant according to anexemplary embodiment of the present invention may comprise: 1) a firstcopolymer comprising the first unit represented by Chemical Formula 1,the second unit represented by Chemical Formula 2, and the third unitrepresented by Chemical Formula 3; 2) a second copolymer comprising thesecond unit represented by Chemical Formula 2 and the third unitrepresented by Chemical Formula 3; 3) one or more photoinitiators; and4) a compound capable of dissolving the photoinitiators. Further, theencapsulant according to an exemplary embodiment of the presentinvention may additionally comprise the reactive silicone-based oligomerrepresented by Chemical Formula 4.

In the encapsulant according to an exemplary embodiment of the presentinvention, the contents on the first copolymer, the second copolymer,the photoinitiator, the compound capable of dissolving thephotoinitiator, the reactive silicone-based oligomer, and the like arethe same as those described above, and thus the specific descriptionthereof will be omitted.

The encapsulant according to an exemplary embodiment of the presentinvention may be formed by using a method known in the art, except thatthe above-described composition for an encapsulant is used. Morespecifically, the encapsulant may be formed by using a method ofapplying, coating, or printing the composition for an encapsulant on asubstrate, but the method is not limited thereto.

The composition for an encapsulant according to an exemplary embodimentof the present invention is characterized in that it is possible tomanufacture an encapsulant which may improve a service life of anorganic electronic device and effectively block oxygen and moisture andthe like, which are introduced from the outside. In addition, thecomposition for an encapsulant according to an exemplary embodiment ofthe present invention is characterized in that by comprising both D-typeand T-type silicone resins in a first copolymer, it is possible toobtain high sensitivity even at low energy particularly during UVcuring, and a cured product having both flexibility and strength isobtained, and simultaneously, effects of outgases on a device areminimized

The encapsulant according to an exemplary embodiment of the presentinvention may be applied to those which encapsulate and protect variousobjects. In particular, the encapsulant may be effective for protectingan object comprising a device which is sensitive to an externalcomponent, for example, moisture and humidity. Examples of the object towhich the encapsulant may be applied comprise: a photovoltaic device, arectifier, a transmitter, or an organic electronic device such as anorganic light emitting diode (OLED); a solar cell; or a secondarybattery, and the like, but are not limited thereto.

For an object to which the encapsulant according to an exemplaryembodiment of the present invention is applied, an inorganic protectivelayer and the encapsulant of the present invention may be multi-layeredto seal the device. The inorganic protective layer and the encapsulantof the present invention may be alternately stacked, but the stacking isnot limited thereto. The inorganic protective layer means an inorganicprotective layer deposited by a vacuum process such as sputtering,evaporation, sublimation, chemical vapor deposition, metal organicchemical vapor deposition, and a combination thereof.

Furthermore, the encapsulant reduces the possibility that the residuesremain inside a sealed structure by minimizing outgases resulting frombyproducts produced in a curing process or unreacted residues in acuring initiator, and the encapsulant exhibits excellent transparency,and as a result, the encapsulant may be formed as a stable encapsulantregardless of the type of organic electronic device such as top emissionor bottom emission.

The organic electronic device may be provided with a typicalconfiguration known in the art, except that an encapsulant is formed ofthe above-described materials. For example, it is possible to use glass,metal or a polymer film, and the like, which are typically used in theart, as a lower or upper substrate. Furthermore, the organic electronicdevice may comprise, for example, a pair of electrodes and an organicmaterial layer formed between the pair of electrodes. Here, one of thepair of electrodes may be formed of a transparent electrode. Further,the organic material layer may comprise, for example, a holetransporting layer, a light emitting layer, an electron transportinglayer, and the like.

MODE FOR INVENTION

Hereinafter, the present specification will be described in more detailthrough Examples. However, the following Examples are provided only forexemplifying the present specification, but are not intended to limitthe present specification.

EXAMPLES <Synthesis Example 1> Preparation of First Copolymer

150 g of TSL8370 (manufactured by Momentive Inc.), 1,250 g of TSL8032(manufactured by Momentive Inc.), 65 g of TSL8031 (manufactured byMomentive Inc.), and 1,600 g of toluene were put into and stirred wellin a 5,000 ml three-necked round flask, and then 100 g of water wasadded dropwise thereto at room temperature, and the resulting mixturewas stirred for about 1 hour.

After the stirring, 700 g of water was additionally added thereto, andthen the temperature was increased to 70° C., and the resulting mixturewas stirred for 2 hours. After the stirring was completed, the siliconelayer and the aqueous layer were separated, the aqueous layer wasdiscarded, and the silicone polymer layer was left behind.

The silicone polymer layer was heated to 80° C., and then 0.5 g of a KOHsolution diluted to 50% was put thereinto, and the resulting mixture waswarmed to 120° C. and stirred for 2 hours. Water was completely removedfrom the final silicone polymer layer, thereby obtaining a firstcopolymer.

As a result of measuring the molecular weight by GPC, a weight averagemolecular weight of 5,000 g/mol was measured by polystyrene standard.

<Synthesis Example 2> Preparation of Second Copolymer

450 g of TSL8032 (manufactured by Momentive Inc.), 100 g of TSL8031(manufactured by Momentive Inc.), and 1,200 g of toluene were put intoand stirred well in a 5,000 ml three-necked round flask, and then 120 gof water was added dropwise thereto at room temperature, and theresulting mixture was stirred for about 1 hour.

After the stirring, 700 g of water was additionally added thereto, andthen the temperature was increased to 70° C., and the resulting mixturewas stirred for 2 hours. After the stirring was completed, the siliconelayer and the aqueous layer were separated, the aqueous layer wasdiscarded, and the silicone polymer layer was left behind.

The silicone polymer layer was heated to 80° C., and then 0.5 g of a KOHsolution diluted to 50% was put thereinto, the resulting mixture waswarmed to 120° C. and stirred for 2 hours, and then a final product wasobtained.

Water was completely removed from the silicone polymer layer, therebyobtaining a second copolymer.

As a result of measuring the molecular weight by GPC, a weight averagemolecular weight of 1,600 g/mol was measured by polystyrene standard.

<Synthesis Example 3> Preparation of Silicone Acrylate Compound A

1,500 g of 1,1,1,3,5,5,5-heptamethyl 3-beta-(3,4-epoxy cyclohexyl) ethyltrisiloxane, 1,000 g of toluene, and 6 g of titanium isopropoxide wereput into and stirred well in a 5,000 ml three-necked round flask.

Thereafter, the temperature was increased to 90° C., and the mixture wasstirred for 8 hours while adding 300 g of acrylic acid dropwise thereto.After the stirring was completed, 30 g of silica (Rhodia MicroPearlZeosil 1165 MP) was added thereto, and the resulting mixture was furtherstirred at room temperature for 2 hours.

After the stirring, the silica was removed by filtering the mixture witha filter. And then, stripping was performed in a vacuum state to removeall the toluene, and then a silicone acrylate compound A was obtained.

Example 1

48 g of the first copolymer obtained in Synthesis Example 1, 19 g of thesecond copolymer obtained in Synthesis Example 2, 19 g of asilicone-based oligomer having the structure of Chemical Formula 7(TSL9706 manufactured by Momentive Inc.), 10 g ofalpha-methacryloxy-gamma-butyrolactone (manufactured by Miwon SpecialtyChemical Co., Ltd.), and 4 g of a photoinitiator (TPO) manufactured byBASF AG were stirred well in a glass vial, thereby obtaining a siliconephotosensitive resin composition.

Example 2

44 g of the first copolymer obtained in Synthesis Example 1, 16 g of thesecond copolymer obtained in Synthesis Example 2, 16 g of asilicone-based oligomer having the structure of Chemical Formula 7(TSL9706 manufactured by Momentive Inc.), 20 g ofalpha-methacryloxy-gamma-butyrolactone (manufactured by Miwon SpecialtyChemical Co., Ltd.), and 4 g of a photoinitiator (TPO) manufactured byBASF AG were stirred well in a glass vial, thereby obtaining a siliconephotosensitive resin composition.

Example 3

48 g of the first copolymer obtained in Synthesis Example 1, 17 g of thesecond copolymer obtained in Synthesis Example 2, 17 g of asilicone-based oligomer having the structure of Chemical Formula 7(TSL9706 manufactured by Momentive Inc.), 10 g ofalpha-methacryloxy-gamma-butyrolactone (manufactured by Miwon SpecialtyChemical Co., Ltd.), and 8 g of a photoinitiator (TPO) manufactured byBASF AG were stirred well in a glass vial, thereby obtaining a siliconephotosensitive resin composition.

Example 4

48 g of the first copolymer obtained in Synthesis Example 1, 19 g of thesecond copolymer obtained in Synthesis Example 2, 19 g of asilicone-based oligomer having the structure of Chemical Formula 7(TSL9706 manufactured by Momentive Inc.), 10 g of 1,6-hexanedioldimethacrylate (manufactured by Sigma-Aldrich Corporation), and 4 g of aphotoinitiator (TPO) manufactured by BASF AG were stirred well in aglass vial, thereby obtaining a silicone photosensitive resincomposition.

Example 5

44 g of the first copolymer obtained in Synthesis Example 1, 16 g of thesecond copolymer obtained in Synthesis Example 2, 16 g of asilicone-based oligomer having the structure of Chemical Formula 7(TSL9706 manufactured by Momentive Inc.), 20 g of 1,6-hexanedioldimethacrylate (manufactured by Sigma-Aldrich Corporation), and 4 g of aphotoinitiator (TPO) manufactured by BASF AG were stirred well in aglass vial, thereby obtaining a silicone photosensitive resincomposition.

Example 6

48 g of the first copolymer obtained in Synthesis Example 1, 17 g of thesecond copolymer obtained in Synthesis Example 2, 17 g of asilicone-based oligomer having the structure of Chemical Formula 7(TSL9706 manufactured by Momentive Inc.), 10 g of 1,6-hexanedioldimethacrylate (manufactured by Sigma-Aldrich Corporation), and 8 g of aphotoinitiator (TPO) manufactured by BASF AG were stirred well in aglass vial, thereby obtaining a silicone photosensitive resincomposition.

Example 7

38 g of the first copolymer obtained in Synthesis Example 1, 34 g of thesecond copolymer obtained in Synthesis Example 2, 19 g of asilicone-based oligomer having the structure of Chemical Formula 7(TSL9706 manufactured by Momentive Inc.), 5 g of the silicone acrylatecompound A obtained in Synthesis Example 3, and 4 g of a photoinitiator(TPO) manufactured by BASF AG were stirred well in a glass vial, therebyobtaining a silicone photosensitive resin composition.

Example 8

29 g of the first copolymer obtained in Synthesis Example 1, 34 g of thesecond copolymer obtained in Synthesis Example 2, 19 g of asilicone-based oligomer having the structure of Chemical Formula 7(TSL9706 manufactured by Momentive Inc.), 14 g of the silicone acrylatecompound A obtained in Synthesis Example 3, and 4 g of a photoinitiator(TPO) manufactured by BASF AG were stirred well in a glass vial, therebyobtaining a silicone photosensitive resin composition.

Example 9

38 g of the first copolymer obtained in Synthesis Example 1, 32 g of thesecond copolymer obtained in Synthesis Example 2, 17 g of asilicone-based oligomer having the structure of Chemical Formula 7(TSL9706 manufactured by Momentive Inc.), 5 g of the silicone acrylatecompound A obtained in Synthesis Example 3, and 8 g of a photoinitiator(TPO) manufactured by BASF AG were stirred well in a glass vial, therebyobtaining a silicone photosensitive resin composition.

Comparative Example 1

48 g of the first copolymer obtained in Synthesis Example 1, 24 g of thesecond copolymer obtained in Synthesis Example 2, 24 g of asilicone-based oligomer having the structure of Chemical Formula 7(TSL9706 manufactured by Momentive Inc.), and 4 g of a photoinitiator(TPO) manufactured by BASF AG were stirred well in a glass vial, therebyobtaining a silicone photosensitive resin composition.

Comparative Example 2

48 g of the first copolymer obtained in Synthesis Example 1, 22 g of thesecond copolymer obtained in Synthesis Example 2, 22 g of asilicone-based oligomer having the structure of Chemical Formula 7(TSL9706 manufactured by Momentive Inc.), and 8 g of a photoinitiator(TPO) manufactured by BASF AG were stirred well in a glass vial, therebyobtaining a silicone photosensitive resin composition.

Comparative Example 3

76 g of the first copolymer obtained in Synthesis Example 1, 20 g of asilicone-based oligomer having the structure of Chemical Formula 7(TSL9706 manufactured by Momentive Inc.), and 4 g of a photoinitiator(TPO) manufactured by BASF AG were stirred well in a glass vial, therebyobtaining a silicone photosensitive resin composition.

Comparative Example 4

76 g of the second copolymer obtained in Synthesis Example 2, 20 g of asilicone-based oligomer having the structure of Chemical Formula 7(TSL9706 manufactured by Momentive Inc.), and 4 g of a photoinitiator(TPO) manufactured by BASF AG were stirred well in a glass vial, therebyobtaining a silicone photosensitive resin composition.

TABLE 1 Constituent component (wt %) Compound capable of dissolvingphotoinitiators Silicone Silicone- acrylate First Second based compoundPhotoinitiator copolymer copolymer oligomer GBLMA HDDA A (TPO) Example 148 19 19 10 0 0 4 Example 2 44 16 16 20 0 0 4 Example 3 48 17 17 10 0 08 Example 4 48 19 19 0 10 0 4 Example 5 44 16 16 0 20 0 4 Example 6 4817 17 0 10 0 8 Example 7 38 34 19 0 0 5 4 Example 8 29 34 19 0 0 14 4Example 9 38 32 17 0 0 5 8 Comparative 48 24 24 0 0 0 4 Example 1Comparative 48 22 22 0 0 0 8 Example 2 Comparative 76 0 20 0 0 0 4Example 3 Comparative 0 76 20 0 0 0 4 Example 4

Characteristics of the compositions prepared in Examples 1 to 9 andComparative Examples 1 to 4 were evaluated, and the evaluation resultsare shown in the following Table 2.

TABLE 2 Adhesion Photo- Storage PI Test curing Modulus Sol- after Rate(@ 25° C., Outgas ubility Curing (%) Mpa) (ppm) Ex- O Cured 93.10 440<100 ample 1 Ex- O Cured 92.70 512 <100 ample 2 Ex- O Cured 99.10 570<100 ample 3 Ex- O Cured 92.00 466 <100 ample 4 Ex- O Cured 91.30 571<100 ample 5 Ex- O Cured 99.22 614 <100 ample 6 Ex- O Cured 96.70 204<100 ample 7 Ex- O Cured 98.40 178 <100 ample 8 Ex- O Cured 99.34 218<100 ample 9 Com- O Cured 56.30 Impossible to >500 parative manufacturetest Ex- specimen ample 1 Com- X Impossible Impossible Impossible toImpossible parative to be to be manufacture test to be Ex- confirmedconfirmed specimen confirmed ample 2 Com- O Cured 67.50 Impossibleto >500 parative manufacture test Ex- specimen ample 3 Com- O Cured55.67 Impossible to >1000 parative manufacture test Ex- specimen ample 4

Experimental Example

1) PI Solubility

For PI solubility, when the mixtures were blended at the compositionsdescribed in the Examples and the Comparative Examples, it wasdetermined whether the photoinitiators were dissolved by observing withthe unaided eye whether the powder-type photoinitiator was alldissolved.

2) Adhesion Test after Curing

A silicone photosensitive resin composition of the present invention wasapplied to have a suitable thickness, for example, a thickness of 4 to40 μm on a substrate subjected to a predetermined pre-treatment by usinga method such as a spin or coating method, a roll coating method, ascreen printing method, and an applicator method, and then the appliedsurface was covered with the same substrate. And then, the substrate wasirradiated with the energy of 1 J at an i-line wavelength of 395 nm. Asa light source used for the irradiation, a low-pressure mercury lamp, ahigh-pressure mercury lamp, a super high-pressure mercury lamp, a metalhalide lamp, an argon gas laser, and the like may be used, and in somecases, an X-ray, an electron ray, and the like may also be used.

Whether the composition was cured or uncured was determined according towhether the substrate was pushed out when pushing the upper substrate byapplying a certain force after the substrate was irradiated with theenergy. When the upper substrate was pushed out and thus separated fromthe lower substrate, it was determined that the composition was uncured,and when the upper substrate was firmly fixed and was not pushed out, itwas determined that the composition was cured.

3) Photocuring Rate (UV Curing Conversion %)

The photocuring rate was confirmed by using FT-IR (IR-Prestige21,manufactured by Shimadzu Corp.). A thin film was applied to have athickness of 5 μm onto a film which does not absorb light at all and hasa transmittance of 100%, and then the surface thereof was covered withthe same film. A test specimen thus obtained was subjected to FT-IRanalysis before the test specimen was cured and after the sample wasirradiated with 1 J (@395 nm LED wavelength) and with 5 J (@395 nm LEDwavelength) to measure the transmittance (%) intensity of thetransmission peak around 1,635 cm⁻¹ (C═C). The photocuring rate wascalculated according to the following Equation 1.

[(B−A)/(C−A)]×100  [Equation 1]

In Equation 1,

A is a transmittance (%) around 1,635 cm⁻¹ (C═C) before the curing, B isa transmittance (%) around 1,635 cm⁻¹ (C═C) after the curing at 1 J, andC is a transmittance (%) around 1,635 cm⁻¹ (C═C) after the curing at 5J.

When the photocuring rate is low, a large amount of uncured residue isproduced, which is responsible for generating a large amount of outgasof the coating film.

4) Storage Modulus

A storage modulus (at 25° C., Mpa) was confirmed by using DMA (Q800manufactured by TA Instruments). A mold with width 5.3 mm×length 17.7672mm×height 2 mm was filled with a sample, and then the sample wasirradiated with UV 1J (@396 nm LED wavelength), thereby manufacturing atest specimen.

The thus-prepared test specimen was analyzed at a temperature risingrate of 3° C. per minute from −40° C. to 80° C. by using DMA, therebyobtaining a storage modulus. Among the storage moduli, the storage valueat 25° C. was taken.

5) Outgas

The outgas was sampled through a pyrolyzer and analyzed by using GC/MS.The outgas was obtained by performing an analysis under the conditionsof a pyrolyzer temperature of 100° C. and a GC oven temperature of 300°C.

The sampling of the sample to be analyzed was analyzed by thin-filmapplying the composition to a thickness of 5 μm, performing UV curingunder a nitrogen atmosphere, and obtaining a material after the curing.The exposure was performed with an energy of 1 J at 395 nm.

As described above, the composition for an encapsulant according to anexemplary embodiment of the present invention is characterized in thatit is possible to prepare an encapsulant which may improve a servicelife of an organic electronic device, and effectively block oxygen andmoisture and the like, which are introduced from the outside.

Further, the composition for an encapsulant according to an exemplaryembodiment of the present invention has a characteristic of improvingthe sensitivity of an encapsulant using the composition for anencapsulant by introducing a novel organopolysilicone-based resin suchas a first copolymer.

In particular, the composition for an encapsulant according to anexemplary embodiment of the present invention may improve thesensitivity during the UV curing by additionally containing a compoundcapable of dissolving a photoinitiator to increase the amount ofphotoinitiator introduced. As described above, the composition for anencapsulant according to an exemplary embodiment of the presentinvention has a characteristic of reducing an amount of outgas of acured product after the curing by increasing the curing rate.

1. A composition for an encapsulant, comprising: 1) a first copolymercomprising a first unit represented by the following Chemical Formula 1,a second unit represented by the following Chemical Formula 2, and athird unit represented by the following Chemical Formula 3; 2) a secondcopolymer comprising the second unit represented by the followingChemical Formula 2 and the third unit represented by the followingChemical Formula 3; 3) one or more photoinitiators; and 4) a compoundcapable of dissolving the photoinitiators:

in Chemical Formulae 1 to 3, R1 is a direct bond, or an alkylene group,R2 to R7 are the same as or different from each other, and areoptionally each independently selected from the group consisting ofhydrogen, an alkyl group, an alkenyl group, an aryl group, a glycidylgroup, an isocyanate group, a hydroxy group, a carboxyl group, a vinylgroup, an acrylate group, a methacrylate group, an epoxide group, acyclic ether group, a sulfide group, an acetal group, a lactone group,an amide group, an alkylaryl group, an alkylglycidyl group, analkylisocyanate group, an alkylhydroxy group, an alkylcarboxyl group, analkylvinyl group, an alkylacrylate group, an alkylmethacrylate group, analkyl cyclic ether group, an alkylsulfide group, an alkylacetal group,an alkyl lactone group, and an alkyl amide group, and a, b, c, and d areeach independently 1 to
 200. 2. The composition of claim 1, wherein R2of Chemical Formula 1 is a vinyl group, an acrylate group, or amethacrylate group.
 3. The composition of claim 1, wherein R3 to R7 ofChemical Formulae 2 and 3 are each independently hydrogen or an alkylgroup.
 4. The composition of claim 1, wherein in the first copolymer, aweight ratio of the first unit represented by Chemical Formula 1:thesecond unit represented by Chemical Formula 2:the third unit representedby Chemical Formula 3 is (1 to 30):(5 to 80):(1 to 30).
 5. Thecomposition of claim 1, wherein in the second copolymer, a weight ratioof the second unit represented by Chemical Formula 2:the third unitrepresented by Chemical Formula 3 is 1:1 to 100:1.
 6. The composition ofclaim 1, wherein the compound capable of dissolving the photoinitiatorscomprises one or more selected from the group consisting of anacrylate-based compound, a methacrylate-based compound, and asiloxane-based compound.
 7. The composition of claim 1, wherein thecompound capable of dissolving the photoinitiators is represented by thefollowing Chemical Formula 4 or 5:


8. The composition of claim 1, wherein based on a total weight of thecomposition for an encapsulant, a content of the first copolymer is 20to 90 wt %, a content of the second copolymer is 1 to 70 wt %, a contentof the compound capable of dissolving the photoinitiators is 0.1 to 30wt %, and a content of the photoinitiator is 0.1 to 10 wt %.
 9. Thecomposition of claim 1, further comprising: a reactive silicone-basedoligomer represented by the following Chemical Formula 6:

in Chemical Formula 6, R9, R10, R12, and R16 are the same as ordifferent from each other, and are each independently a direct bond oran alkylene group, R8, R11, R13, R14, R15, and R17 are the same as ordifferent from each other, and are optionally each independentlyselected from the group consisting of hydrogen, an alkyl group, analkenyl group, an aryl group, a glycidyl group, an isocyanate group, ahydroxy group, a carboxyl group, a vinyl group, an acrylate group, amethacrylate group, an epoxide group, a cyclic ether group, a sulfidegroup, an acetal group, a lactone group, an amide group, an alkylarylgroup, an alkylglycidyl group, an alkylisocyanate group, an alkylhydroxygroup, an alkylcarboxyl group, an alkylvinyl group, an alkylacrylategroup, an alkylmethacrylate group, an alkyl cyclic ether group, analkylsulfide group, an alkylacetal group, an alkyl lactone group, and analkyl amide group, and e is 1 to
 100. 10. The composition of claim 9,wherein Chemical Formula 6 is represented by the following ChemicalFormula 7:


11. The composition of claim 9, wherein based on the total weight of thecomposition for an encapsulant, the content of the first copolymer is 20to 60 wt %, the content of the second copolymer is 10 to 30 wt %, thecontent of the photoinitiator is 0.1 to 10 wt %, the content of thecompound capable of dissolving the photoinitiators is 5 to 30 wt %, andthe content of the reactive silicone-based oligomer is 5 to 30 wt %. 12.An encapsulant formed by using the composition for an encapsulantaccording to claim
 1. 13. An organic electronic device comprising theencapsulant according to claim 12.